Process for the production of an indene phenol



Patented July 1, 1947 PROCESS FOR THE PRODUCTION OF AN INDENE PHENOLFrank J. Soday, Baton Rouge, La., 'assignor to The United GasImprovement Company, a corporation of Pennsylvania No Drawing.Application May 17, 1943, Serial No. 487,338

.5 Claims. 1

This invention pertains generally to a process for the production ofreaction products of an indene type compound and a phenol, and pertainsparticularly to the production of indene phenol.

The invention pertains more particularly to the production of compoundsof this type capable of being further reacted with aldehydes generallyto obtain resins of the phenol-aldehyde type which are soluble in theusual drying oils, such as linseed and tung oils.

There is thus made available oil soluble resins of thephenol-aldehydetype which are ideally suited for incorporation in liquidcoating compositions, such as varnishes, lacquers, paints and the like,either alone or in combination with other resins.

The outstanding characteristics of the phenolaldehyde type of resin arethus made available in the liquid coating composition field.

Since the more common phenol-aldehyde resins are not soluble in dryingoils to a satisfactory degree, the use of such resins in theliquid=coating composition field is limited.

However, after having acquired the quality of unusual oil solubility,the field of use of resins 'of the phenol-aldehyde type is greatlyextended.

The reactionof indene with phenol with the production of substitutedphenols, has been described in the prior art.

In the processes thus described, the reaction between indene and phenolgenerally is brought about by the use of sulfuric or acetic acids ascatalysts.

Because of the relatively low yields obtained and the relatively largeamount of catalyst employed, which adds greatly to the cost, theseprocesse have not achieved any industrial importance.

I have discovered that the indene-phenol type compounds generally andindene phenol particularly may be produced with high yields of excellentquality by reacting a hydrohalide of indene with a phenol in thepresence of a suitable catalyst.

In addition to pure indene, commercial and technical grades thereof, Imay also employ fractions and/or mixtures containing any desiredproportion of indene in the practice of my invention.

The use of light oil indene fractions, such as those obtained by thepyrolysis of petroleum or of petroleum hydrocarbons at temperaturesabove 1100 F. and more particularly above 1300 F. in

the vapor phase in the presence of steam, is preferred, as suchfractions contain very little, if any, coumarone, or other oxygen,nitrogen, or sulfur containing unsaturated impurities of the typecommonly found in coal tar fractions.

I generally prefer to employ indene fractions boiling mainly in therange of 175 to 190 C. and more particularly in the range of 178 to 1850.

While fractions containing almost any desired proportion of indene maybe used in the practice of my invention, I prefer to employ fractionscontaining at least 30% indene and more particularly at least 50%indene. Excellent results are obtained by the use of fractionscontaining at least 70% indene.

Substituted indenes, such as the methyl indenes also may be employed inthe practice of my invention, Light oil methyl indene fractions obtainedfrom the above source and boiling mainly in the range of 190 to 220 C.are preferred. Examples of phenols are phenol itself, other mono orpoly-valent phenols, their substitution products such as the halogen,sulfo, alkyl, aryl,

,aralkyl, nitro, carboiwl, and azo-nuclear substitution products, andphenolic compounds in general. Within this class of compounds areincluded. cresol, amino-phenols, nitro-phenols, chloro-phenols, thymol,naphthols, pyrocatechol,

\ .resorcinol, hydroquinone, pyrogallol, oxyhydroquinone,phloroglucinol, carvacrol, quinol, xylenol, guaiacol, orcinol, mesitol,pseudocumenol, toluhydroquinone, alpha naphthol, and beta naphthol,aswell as mixtures containing one or more of these compounds.

Low temperature tar phenols and mixtures of phenolic compounds also maybe used. These are contained, for example, in tar oils or alcohols, suchas benzyl alcohol, oracids, such as acetic acid. The phenolic compoundsmay be used in the pure state, or as crude materials, or as technicalmixtures.

Phenolic ethers also may be used in the process.

The foregoing compounds will be referred to herein as phenoliccompounds" or phenols.

In carrying out the reaction between an indene hydrohalide and a phenol,I prefer to employ as a catalyst one or more metal halides which termincludes the boron halides and the complexes of all of the foregoinghalides, and particularly the organic solvent complexes of said halides.

Examples of .metal halides are aluminum chloride, zinc chloride, ferricchloride, boron trifluov dride; metal salts, such as potassiumbisulphate,

aluminum sulfate, aluminum phosphate, and

deposited on carriers, such as the previously listed contact materialsor other substances such as barium sulfate, pumice, asbestos and silica.

The indene hydrohalide to be used as starting material may be obtainedfrom any suitable source known in the art, or may be prepared, forinstance, by the addition of a selected hydrogen halide, such ashydrogen chloride to indene.

In case the indene hydrohalide is to be prepared, the indene to behydrohalogenated may be either in concentrated form or in the form of afraction or solution.

For example, indene may be obtained from light oil produced in themanufacture of gas, such as carburetted water gas or oil gas. Theconcentration of indene in a fraction is frequently relatively low,particularly in the case of forerunnings and afterrunnings, due to thedifllculty of concentrating by distillation compounds which are capableof being polymerized by heat.

All or such fractions lend themselves to the production of indenehydrohalides.

The indene hydrohalides may be separated from such fractions, say bydistillation, or may be employed without such separation.

As a general rule, the isomeric indene hydrohalides are produced inthis, way.

However, the reaction might be carried out in a manner such that one orthe other form predominates.

If desired, the isomeric compounds may be separated prior to theirreaction with the phenol, or they may be reacted with the phenol withoutprevious separation.

There are several possible reactions between a particular indenehydrohalide and a phenol.-

The reaction between indene hydrohalide and phenol presumably takesplace in the following manner.

p-substituted indene phenol indene hydrophenol halide H Catalyst I H 01indene hydrophenol halide bsubstituted indene phenol Presumably verylittle, if any, meta substituted compound is formed.

The isomeric indene hydrohalide also may react with phenolic compoundsin a similar manner.

01 Catalyst indene hydrohenol halide p p'-suhstituted idcne phenol Theproduct shown in reaction (3) "is the para substituted form.

The ortho substituted form also may be formed in this reaction as shownin the following equation.

Presumably very little, if any, meta substituted compound is formed.

The reaction between an indene hydrohalide and a phenol may also resultin the production of diand poly-substituted derivatives, as shown, forexample, by the following equation.

H H 0H Catalyst p-substituted idene phenol indene hydrohalide 0-,p-substituted indene phenol In addition, indene hydrohalides may reactwith phenolic compounds to give phenolic ethers, as shown in thefollowing equation.

Catalyst indbllllfl hydrophenol alid indene phenyl ether Accordingly, aseparation step, such as by distillation, usually follows the reactionif it is desired to employ the indene phenol apart from the othermaterials.

Furthermore, while the mono-substituted derivatives, namely indenephenols, normally predominate in the reaction product over the diandpoly-substituted derivatives, it is possible to vary the proportion ofone to the other by varyin the proportion of starting materials.

For example, when phenol is in excess, indene phenol predominates in thereaction product,

be combined in any desired manner whether] or not in concentrated form,or in solution or ad- 'mixture.

Contact between the materials may be effected v in any manner known inthe art. In this connection, reference is had to the very large numberof different ways of contacting'reactants in the prior art.

However, it is preferred when the chosen phenol is in excess to add thechosen indene hydrohalide to a mixture of the phenol and the catalyst.

On the other hand, when the chosen indene hydrohalide is in excess, itis preferred to add the chosen phenol to a mixture of the indenehydrohalide and the catalyst.

The reaction may be carried out at almost any desired temperature whichmay vary during the reaction.

, I find, for example, that excellent results are secured by conductingthe first part of the reaction at moderate temperatures, for example,between and 100 0., followed by higher temperatures, such as between 100and 200 C.

Temperatures between 40 and 55 C. for the initial reaction followed bytemperatures between 140 and 150 C. for the flnalreaction, are found tobe particularly suitable.

In case the temperature is held uniform, temperatures between 10 and 180C. are preferred.

While the reaction is customarily carried out at atmospheric pressure,it will be understood that sub-atmospheric and super-atmosphericpressures may be employed if desired.

' The quantity of catalysts employed may also be varied over fairly widelimits. As an example, 0.1% to 10% by weight of catalyst to the combined weight of both reactants will be found suitable.

When using acid-acting metal halide catalysts -or complexes thereof,0.1% to by weight of catalyst to, the combined weight of both reactantsis found particularly suitable.

In order to speed up the reaction and carry it further to completion,steps may be taken to remove hydrogen halide from the sphere of thereaction, such as by absorption, or by stirring or by passing an inertgas through the reaction mass. f

The hydrogen halide thusdisplaced from the reaction mass may, of course,be recovered and reused in the hydrohalogenation of indene.

However, considerable quantities of hydrogen halide escape from thereaction mass without external aid.

, The following example will further illustrate the process.

EXAMPLE 1 A light oil indene fraction, obtained by the fractionation oflight oil obtained from oil gas and containing one mole is placed in aone liter three-neck flask equipped with a stirring device. The flaskand its contents are cooled to a temperature of 0 C. and a moderatestream of dry hydrogen chloride introduced into the flask. The reactionis continued for a period of 24 hours, during which time approximatelythe theoretical amount of hydrogen chloride toconvert the indene presentto indene hydrohalide is absorbed.

The excess hydrogen chloride is removed from the indene fraction bydistilling under reduced pressure.

The residual material is washed with water, dried, and distilled in aVigreux column to remove the unchanged hydrocarbons present.

The residue then is fractionated.

The indene hydrohalide obtained is slowly added with good agitation to amixture of one mol gram of phenol, 3.0 grams of aluminum chloride, and200 grams of freshly dried n-heptane. The reaction mixture is agitatedfor a period of 6 hours at room temperature, followed by agitation foran additional period of one hour at a temperature of 100 C. During thefirst hour of the reaction, considerable quantities of hydrogen chlorideis given off by the reaction mixture.

prepared from the hydrogen halide liberated during the course of thereaction with the phenol. In this instance, a small amount of indenehydrohalide may be added to the reaction mass to start the reaction,followed by the addition of the remainder of the indene.

On the other hand, hydrogen halide may be supplied by bubbling itthrough the reaction mass.

This is illustrated in Example 2.

EXAMPLE 2 A mixture of 329.5 grams of phenol, 2 grams of an 83.7% indenefraction (containing 1.7 grams of indene) and 1.7 grams of aluminumchloride was placed in a one-liter three-neck flask at room temperature.Gaseous hydrogen chloride was passed through this mixture for a periodof one -minute, after which the addition of hydrogen chloride wasdiscontinued. A gram portion of the same indene fraction (containing108.8 grams of indene) was slowly added to the mixture during a periodof one hour. The mixture was continually agitated during thi time andthe temperature was maintained within 40-55" C. The temperature then wasraised to -150 -C. during a period of 20 minutes, and maintained at thispoint for an additional period of 2 hours.

The catalyst component of the solution then was neutralized with a 20%solution of sodium carbonate containing 3.9 grams of NazCOa. The waterlayer was separated and the residue distilled in a modified Claissenflask under reduced pressure.

A total of 149.5 grams of idene phenol (74.8% yield), with a boilingrange of 153-200C. 4.5 mm. was obtained. A total of 23.3 grams of thehigher boiling (200-247" C. 23.3 mm.) diindene phenol also was obtained.

The indene phenol was obtained as a light colored, viscous liquid whichslowly crystallized on standing, forming colorless crystals.

A further modification of this invention resides in the preparation ofindene phenol by the reaction of indene and a phenol in the presence ofan acid-acting metal halide and moisture, of which a trace is frequentlysuflicient. It is found that the minute quantity of hydrogen halideliberated due to the presence of even a trace of moisture issufiicient'to initiate the reaction.

This is illustrated in the following example: EXAMPLE 3 A very slightlymoist indene fraction obtained by the distillation of light oil from oilgas, and containing one mol of indene is slowly added with goodagitation to a mixture of one mol of phenol and 1.56 gram of aluminumchloride during a period of one hour at a temperature of 4055 C.

The boiling range of theindene phenol listed in the foregoing examplesdoesv notnecessarily represent the true boiling range of the materialdue to excessive superheating during the distillation process.

The mechanism proposed for this reaction is of the chain type. Indenehydrohalide reacts with a phenol to give substituted phenolic compoundswith the liberation of hydrogen halide, which in turn reacts with moreindene to produce further indene hydrohalide, thus perpetuating thereaction.

A further extension is the addition of a Small amount of some otherhydrocarbon halide to the reaction mass with or Without the presence ofmoisture to initiate the reaction'by the liberation of a small amount ofhydrogen halide, which in turn reacts with the indene present to formindene hydrohalide, the formation of which is then perpetuated.

The degree of contamination resulting from starting the reaction with ahydrocarbon halide becomes less significant, the larger the quantitiesof indene hydrohalide and phenol reacted.

On the other hand, larger quantities of alkyl or aryl halide may beemployed to initiate the reaction, in which case the product eventuallyobtained will comprise a mixture of indene substituted phenols andphenolic ethers, as Well as subr stituted phenols and phenolic e thersderived from the aryl or alkyl halide.

The product thu obtained may be, in turn, reacted as such with analdehyde to form a resin, or its components may bepreviously separatedsuch as by fractional distillation at reduced pressures, and then one ormore separately reacted with an aldehyde.

The use of a substantial quantity of a hydrocarbon halide other thanindene halides permits the preparation of substituted phenols with awide variety of different properties, since the hydrocarbon halide maybe selected from a wide variety of different compounds both alkyl andaryl.

Furthermore, the properties may be varied considerably by varying therelative proportions of hydrocarbon halide and indene hydrohalide.

Indene phenol may be isolated from the reaction mass if desired, by anymeans known in the art. For instance, it may. be isolated by washing outany excess phenol followed by fractional distillation under reducedpressure.

Inden'e phenol also may be isolated directly by fractional distillationunder reduced pressure.

When using fractional distillation fairly low pressures are recommended,such as .pressures of the order of from 1 to 2Q mm. absolute.

However, the reaction product may be reacted with an aldehyde withoutprevious separation into component parts.

For example, it may be reacted with formaldehyde or formaldehydeyielding substances, such as hexamethylenetetramine, either with orwithout the addition of a further coupling agent, for example, a smallamount of oxalic acid.

Usually, it will be found that a further coupling agent is not requiredsince the residual hydrogen halide present in the reaction productserves as a very efi'ective coupling agent.

The production of phenol-formaldehyde type resins is illustrated by thefollowing examples.

EXAMPLE 4 EXAMPLE 5 A standard 15 gallon varnish was prepared from thisresin in the following manner.

Formula Parts Resin 12.2 China-wood nil 14.0 Solvent naphtha V. M. & P26.2 Drier (cobalt, manganese and lead drler) 1.0

The mixture of resin and China-wood oil was heated in a copper beaker toa temperature of 400 F. during a period of 20 minutes. The mixture thenwas heated to a temperature of 560 F. during a period of 10 minutes, andheld at this temperature for an additional period of 3 minutes. It wasallowed to cool to 535 F., held at this temperature for a period of 6minutes, chilled to 400 F. (by partially immersing the beaker in water)and reduced by the addition of the solvent naphtha. The drier wasstirred into the varnish when it reached room temperature.

The product was a clear, light colored varnish with excellent coatingproperties. It may be used to coat metals, wood, and other surfaces,such as those of beverage and food containers.

The substituted phenolic compounds made in accordance with my invention,may be reacted with any of the aldehydes commonly used for thepreparation of phenol-aldehyde type resins.

In the case of formaldehyde, gaseous formaldehyde, aqueous formaldehydesolutions of different concentrations, polymerization products offormaldehyde, such as trioxymethylene, polyoxymethylenes, orparaformaldehyde, or formaldehyde yielding substances, such ashexamethylene 'tetramine may be employed.

The resin forming reaction, if desired, may take place in the presenceof inert substances, such as plasticizers, fillers, pigments, coloringbodies, and the like.

Furthermore, the resin-forming reaction may be carried out in thepresence of fats; oils such as drying oils, linseed oil, tung oil,castor oil, oiticica, oil; waxes, such as m'ontan wax; natural resins,such as colophony, kauri, copal, dammar; and synthetic resins, such ascoumarone resin, urea-formaldehyde resin and the like.

The resinification reaction may be carried out in two or more stages, ifdesired.

Thus, a product may be produced by a preliminary condensation reactionand the melting point raised by subsequent heating.

The products resulting from the resinification reaction may varyconsiderably in their properties, such as from resinous viscous-liquidsto solid substances of different degrees of hardness, depending upon thechoice of the reactants used for resinification and resinificationconditions such as temperature and reaction time.

As pointed out above, the resins thus produced are ideally suited forincorporation in liquid coating compositions, .such as varnishes,lacquers, paints, and the like, inview of their unusual high solubilityin the customary drying oils, such as linseed oil and tuna oil.

My process is subject to considerable variation.

For instance, the production of indene phenol and the resiniflcationreaction may take place simultaneously, in which case the aldehyde mightbe added to the reaction mass simultaneously with the other reactants orthe aldehyde might be added at any other time or manner, such as at anystage after the reaction for the production of indene phenol hascommenced.

This reaction usually does not require a coupling agent, however, acoupling agent may be added, if desired.

Generally speaking, coupling agents suitable for use herein may be 01'any type and either acid; neutral or alkaline in character.

From the foregoing description and examples, it will be seen that thehydrohalide oi! indene (which is also referred to for convenience asindene hydrohalide) may be previously formed or generated in situ.Therefore, for the purposes of the claims, the term indene hydrohaiideunless otherwise modified, is intended to mean a hydrohalide of thischaracter whether-previously formed, or formed in situ.

It is to be understood that the above particular description is by way91' illustration and that, broadly speaking, changes, omissions,additions,

substitutions and/or modifications might be" made within the scope ofthe claims without departing from the spirit of the invention which isintended to be limited only as required by the prior art.

I claim:

1. A process for the production of an indene phenol from indene whichcomprises reacting indene with a hydrohalide to produce indenehydrohalide and reacting the indene hydrohalide thus produced withphenol in the presence of aluminum chloride to produce said indenephenol.

2. A process for producing an indene phenol from indene which comprisesreacting indene with hydrogen chloride to produce indene hydrochlorideand reacting the indene hydrochloride thus produced with phenol in thepresence of aluminum chloride to produce said indene phenol.

3. A-process for the production of an indene phenol comprisingcontacting a light oil indene fraction with hydrogen chloride to formindene hydrochloride, reacting said indene hydrochloride with phenol inthe presence of aluminum chloride, and separating an indene phenol fromthe reaction mixture.

4. A process for the production of indene phenol comprising admixingphenol with a relatively small amount of an indene hydrochloride and a.relatively small amount of aluminum chicride, adding a light-oil indenefraction to said mixture with agitation while maintaining thetemperature at about 40 to C., thereafter raising the temperature toabout to C. and continuing the reaction for a desired period, andseparating indene phenol from the reaction mixture.

5. A process for the production of indene phenol comprising admixingphenol with a light oil indene fraction containing a relatively smallamount of moisture in the presence of a relatively small amount ofaluminum chloride while maintaining the temperature at about 40 to 55C., thereafter raising the temperature to about 140 C. to 150 C. andcontinuing the reaction for a desired period, and separating indenemixture. FRANK J. SODAY.

REFERENCES CITED The following references are of record in the file ofthis patent:

* UNITED STATES PATENTS phenol from the reaction Number Name Date1,754,052 Rosenthal Apr. 8, 1930 2,017,877 Turkington Oct. 22, 19352,242,250 Honel May 20, 1941 OTHER REFERENCES courtot, Comptes rendues.vol. 187, pp. 661-3 (1928). (Copy in Scientific Lib.)

